Cyclization of aliphatic hydrocarbons



1958 CHlA-CHEN c. KANG ETAL 2,849,504

CYCLIZATION OF ALIPHATIC HYDROCARBONS Filed Feb. 10, 1954 NAPHTHAFRACTION SEPARATION ZONE NORMAL PENTANE REMAINDER OF NAPHTHACYCLICITZATION ZONE 6 CYCLOPENTANE HYDROFORMING HIGH CTANE ZONE GASOLINEl INVENTOR CHIA- CHEN C. KANG JOHN M. MC CREA BY M ATTORNEY UnitedStates Patent O CYCLIZATION F ALIPHATIC HYDROCARBONS Chia-chen C. Kang,Newark, and John M. McCrea, Jersey City, N. J., assignors to The M. W.Kellogg Company, Jersey City, N. J., a corporation of DelawareApplication February 10, 1954, Serial No. 409,504

19 Claims. (Cl. 260--666) This invention relates to the cyclization ofacyclic bydrocarbons, and more particularly, it pertains to a method ofproducing cyclopentane and/or substituted cyclopentane from acyclichydrocarbons.

Cyclopentane and/ or alkyl substituted cyclopentane are useful as motorfuels, or in the case of the substituted cyclopentanes, they can be usedas starting materials for the production of aromatics. Although thesecyclic compounds have particular use in the petroleum field, thus fartheir exploitation has been limited by virtue of the absence of asatisfactory method of manufacture. By

means of this invention, it is proposed preparing these cyclic compoundsby a method which is commercially attractive.

An object of this invention is to provide a method of producingcyclopentane and/or the alkyl substituted derivatives thereof.

Another object of this invention is to cyclicize acyclic hydrocarbonsfor the production of cyclopentane and/ or alkyl substitutedcyclopentanes.

Still another object of this invention is to cyclicize a low boilingfraction of petroleum naphtha and subject the resulting cyclic productto hydroforming treatment.

Other objects and advantages of this invention will become apparent fromthe following description and explanation thereof.

By means of this invention, it is contemplated cyclicizing an acyclichydrocarbon by the method which comprises subjecting said hydrocarbon totreatment with a catalyst containing about 1 to about 50% by weight ofplatinum, at .a temperature of about 250 to about 420 C., preferably,about 300 to about 380 C., a pressure of about 1 atmosphere to about 200p. s. i. g., a weight space velocity of about 0.001 to about 2 and for aperiod sufficient to produce a cyclopentane compound. It should beunderstood for purposes of this specification and the appended claimsthat the expression cyclopentane compound covers genericallycyclopentane and alkyl substituted cyclopentane.

The starting material to be used for the preparation of the cyclopentanecompound is an acyclic hydrocarbon containing at least five carbon atomsand the starting compound can have up to about fifteen carbon atoms. Thecyclopentane compound is readily prepared from acyclic hydrocarbonscontaining five to about nine carbon atoms. The lower molecular weighthydrocarbons can be obtained as single compounds or as mixtures thereoffrom petroleum stocks, e. g., naphtha. The higher molecular weighthydrocarbons can also be used as single compounds or as mixtures ofvarying chain length, and these can be obtained from petroleum stocks.In one aspect of this invention, it is contemplated subjecting a naphthafraction to a separation treatment whereby a C and/or C fraction isremoved therefrom, and this fraction is treated in accordance with themethod of this invention prior to being charged to a hydroformingoperation for the production of aromatics. Alternatively, thecyclopentane compound can be blended with Patented Aug. as, 1958 thereformed product to produce a finished material of improved quality. Inany event, the starting material for the production of cyclopentanecompounds can be a straight chain material, isomers thereof, or mixturesof the foregoing in the same or varying chain lengths. For reasonsexplained hereinafter, it is preferred to use saturated acyclichydrocarbons as starting materials, however, mixtures of olefins andsaturated hydrocarbons can be used with less satisfactory results.

The invention, as illustrated in the single figure draw- 1ng, may berepresented by a naphtha fraction which is passed through line 1 into aseparation zone 2, wherein normal pentane or some other acyclichydrocarbon is separated from the remainder of the naphtha and withdrawnthrough line3. The normal pentane is passed to a cyclization zonewherein it is contacted with a catalyst containing 1 to 50 percent byweight of platinum at a temperature of about 250 C. to about 420 C., apressure of about 1 atmosphere to about 200 p. s. i. g., a weight spacevelocity of about 0.001 to about 2 and for a period of time suflicientto produce a cyclopentane compound. The cyclopentane compound iswithdrawn through line 5.

The remainder of the naphtha is passed through line 6 to hydroformingzone 7 wherein it is treated to produce the high octane gasoline whichis withdrawn through line 8. The cyclopentane product in line 5 is alsousually introduced into the hydroforming zone 7, although if desired itmay bypass the hydroforming zone 7 through line 9 and may beblended'directly with the high octane gasoline in line 8.

The catalyst employed for this invention comprises about 1 to about 50%by weight of platinum supported on an adsorptive carrier material.Preferably, the platinum compound is about 5 to about 25% by weight ofplatinum, based on the total weight of the catalyst. The adsorptivecarrier material can be, for example, an inorganic metal oxide gel, e.g., alumina, silica, etc., or charcoals derived from animal'or vegetablematter. The charcoals are the best suited support material for thecatalyst by reason of their high adsorptivity. The charcoals areemployed in the activated form and comprise, for example, coconutcarbon, norite, etc. It appears that the cyclization reaction is bestcatalyzed by a support material which possesses high adsorptivity,apparently for the reason that it furnishes better contact between thecatalytic metal, platinum, and the acyclic hydrocarbon than is possiblewith less adsorptive carrier materials. The charcoals appear to have thebest carrier material properties from this standpoint, as shown by theyield of cyclopentane. However, it should be understood that this theoryis advanced as a possible explanation, and it should not be interpretedas a limitation on the scope of this invention.

The catalyst is prepared by combining a platinum compound, e. g.,chloroplatinic acid, platinic chloride, platinum sulfide, platinumammine complex, platinum polysulfide, etc., with the carrier materialand decomposing the platinum compound to a metallic residue. Thedecomposition reaction can be effected by calcination or reduction. Thecalcination treatment involves heating the catalyst mixture to atemperature of at least about 400 F., more usually, about 600 F. toabout 1450 F., and for a period of about 1 to 15 hours, more usually,about 2 to 8 hours. The reduction reaction can be effected with citricacid, hydrogen or hydrazine, or other reducing agents in general,particularly those of gaseous form. It is preferred to employ'a hydrogencontaining gas for the reduction reaction, because this materialfurnishes an excellent catalyst. Prior to the decomposition reaction, itmay be desirable to dry the catalyst mixture in order to remove anywater which is present by reason of the method of combining theingredients. The drying step can be conducted at a temperature of about150 to about 400 F., more usually, about 175 to about 300 F., and for aperiod of about 3 to about 60 hours.

The temperature at which the cyelization reaction takes place is in therange of about 250 to about 425 F., preferably, about 300 to about 380F. As the temperature is raised above the preferred upper limit there isa noticeable drop in yield of cyclopentane compound, hence, indicatingthat the cyelization reaction is definitely favored by lowertemperatures than are normally encountered in conventional hydroforming.Within the temperature range described above, the cyelization reactioncan be effected at pressures, e. g., about 1 to about 70 p. s. i. 21.,preferably, about 14 to about 40 p. s. i. a. The quantity of hydrocarbonfeed processed relative to the amount of catalyst present in thereaction zone is measured on a weight space velocity, defined as thepounds of liquid feed charged to the reaction zone on an hourly basisper pound of catalyst present therein. The weight space velocity variesfrom about 0.001 to about 2, preferably, about 0.1 to about 0.5. Theconditions given above apply to a fixed bed system or a moving bedsystem. In the case of a fixed bed system, the reaction period variesfrom about 0.5 to 100 hours, more usually, about 2 to about 36 hours. Amoving bed system involves a catalyst to oil ratio of about 0.001 toabout 5. The unreacted acyclic hydrocarbon can be recycled to thecyelization zone in any amount which is desired.

The catalyst may lose activity after processing for a given period oftime and the activity can be restored by treatment with a hydrogencontaining gas. The regeneration treatment involves pure hydrogen or agas containing about 40 to 95% by volume of hydrogen, such. as the gasproduced in a hydroformer. The regeneration treatment is conducted at atemperature of about 250 to 420 C., more usually, about 300 to about 380C., and for a period of about 0.5 to about 30 hours, more usually, about1 to about 8 hours. The regeneration pressure can be in the same rangeas given above for the cyelization reaction. The regeneration gas, on ahydrogen basis, is fed to the catalyst zone at volumetric spacevelocities ranging from about .5 to about 40 V /hn/V The cyelizationreaction is conducted preferably with a hydrogen treated catalyst. Thecatalyst can be treated by one or more of several methods, viz., (1)prior to introducing the hydrocarbon feed to the reactor, the catalystcan be treated with hydrogen; (2) during the reaction phase, thehydrogen can be introduced into the reactor as a separate stream or incombination with the hydrocarbon feed; (3) by the method involving thecombination of (1) and (2); etc. It appears that hydrogen prevents theformation of olefinic materials and that these materials adverselyinfluence the cyelization reaction. These conclusions appear to findsupport in several ex periments made in the presence of helium, with andwithout a helium flush of the catalyst prior to the reaction cycle, aswell as an experiment in which an olefin was added to the hydrocarbonfeed. In every case where the above were tried, the cyclopentanecompound yield decreased significantly. The quantity of hydrogen whichis used in general varies from about 1 to about 1000 standard cubic feetof hydrogen (measured at 60 F. and 760 mm.) per barrel of hydrocarbonfeed (1 barrel equals 42 gallons), abbreviated as s. c. f. b. In thepreferred operation where the hydrocarbon feed is substantially free ofolefins, the hydrogen feed can be about 5 to about 50 s. c. f. b. Whereolefins are present in the feed, a higher hydrogen rate can be used,viz., about 100 to about 1000 s. c. f. b. in order to hydrogenateolefins and counteract their adverse influence on catalyst activity.

As previously indicated, the present invention can be used for theproduction of single cyclopentane compounds, e. g., cyclopentane, ormixtures of such compounds. An excellent application of this inventioninvolves it being used with a commercial hydroformer. In this case, thenaphtha feed to the hydroformer is subjected to a separation treatmentwhereby the C and/or C hydrocarbons are removed therefrom. The higherboiling fraction is passed to the hydroformer; whereas the C and/or Chydrocarbons are charged to a cyelization reactor which is operated inaccordance with the present invention. The reaction product from thecyelization reactor is treated for the separation of cyclopentanecompounds, and the remaining unreacted C and/or C hydrocarbons arerecycled for further cyelization treatment. The cyclopentane compoundsare charged to the hydroformer. Recycling of unreacted acyclichydrocarbon can be used whether the cyclicized product is passed to ahydroformer or not. The net hydrogen produced in the hydroformer can beused for treatment of the catalyst in the cyelization reactor. Thehydroformer to which the cyclopentane compounds are charged can be oneinvolving the use of a reforming catalyst possessingdehydrogenation-hydrogenation properties or aromatizationcharacteristics, e. g., a group V or VI metal oxide or sulfide, e. g.,M00 chromia, etc.; a heteropoly acid in which the outer acid formingelement is, for example, molybdenum; or a platinum or palladiumcatalyst. The catalytic element is supported on a carrier material. e.g., alumina, silica, pumice, zinc spinel, etc., and it comprises about0.05 to about 30% by weight of the total catalyst. The reaction isconducted at a temperature of about to about 1025 F., a pressure ofabout 25 to about 1000 p. s. i. g., a weight space velocity of about 0.1to about 15, a catalyst to oil ratio (where appropriate) of about 0.1 toabout 10, and a hydrogen rate of about 1000 to about 10,000 s. c. f. b.The naphtha feed is one which contains C or C acyclic saturatedhydrocarbons or both, and the naphtha was an end point of about 320 toabout 460 F.

Having thus described generally the present invention, reference will behad to specific examples for a fuller understanding thereof.

The catalyst employed in the following examples were prepared asfollows: 1

CATALYST I 45 grams of 6-14 mesh activated coconut charcoal werecombined with an aqueous solution containing 21 grams of H PtCl .6H O.The mixture was heated by means of a steam bath until substantially allthe water was removed. The dried solids contained about 15% by weight ofplatinum metal (present in the compound). The dried catalyst mass wasthen placed in a test unit reactor and flushed with hydrogen. Followingthe flushing step, the catalyst was activated by raising the temperatureto 300 C. over a period of 9 hours with hydrogen flushed through thereactor. The finished catalyst was maintained in an active state by ahydrogen atmosphere at a temperature of 290 C.

CATALYST II 50 grams of a catalyst containing 0.3% by weight of platinumsupported on alumina were combined with an aqueous solution containing26.1 grams of H PtCl .6l-I O. The mixture was dried in an oven at 240 F.until substantially all of the water was removed. On a platinum basis,the catalyst contained 15% by weight of platinum. The dried catalyst wasplaced in a suitable reactor and then flushed with hydrogen. Thecatalyst was activated by maintaining a flow of hydrogen thereover andcontrolling the temperature at 300 C. for a 9 hour period. Thereafter,the catalyst was maintained in a hydrogen atmosphere at 290 C. prior toactual use.

In order to determine the eifect of hydrogen on the cyelization reactor,two experiments were performed, namely, one in which helium was employedfor treating the catalyst and the other in which hydrogen wassubstituted for helium. The results of these tests are given in Table I.

Table I Run No 1 2 Catalyst I I. Hydrocarbon 2,2,4-trimethyl-2,2,4trimethy1- 2gentane. pentane.

He flush, mols Product, mol percent (UCgHm Table II Run No 1 2 3Catalyst I I II. Feed n-Pentane.. 2,4-dimethyl- 2,4-dimethylpentanepentane. Temperature, 0... 32

Pressure, p. s. i. g.--..-. Space veL, Wo/hr./W.,-. H flush, mols 06Product (mols per mol of feed reacted):

Gyclopentane 1,3-dimet11ylcyclopentane.

In Table II above, it is noted that the platinum catalyst containingcharcoal as the support material was very active in cyclizing n-pentaneto cyclopentane. Further, runs 2 and 3 furnish a comparison betweencatalysts containing the two different support materials. It is apparentthat the catalyst containing activated charcoal as the support materialwas significantly more active than the catalyst containing alumina as asupport material.

Additional experiments were performed in order to determine theeiiectiveness of the present invention with respect to higher straightchain saturated hydrocarbons. The results of these experiments are givenin Table III below.

Table III Run No 1 2 3 Catalyst... I.

eed n-Hexane. n-O etane. Temperature, 0. 5 325.

Pressure, p. s. i. g.

flush, mols Product (mols per mol of reacted feed):

Methylcyclopentane. 0 -cyc1opentane---- C -cyclop entane fractioncontaining a straight chain hydrocarbon selected from the groupconsisting of a C hydrocarbon, a C hydrocarbon and mixtures thereof to aseparation treatment whereby a straight chain hydrocarbon is removedtherefrom, contacting 'at least the remainder of the naphtha fractionwith a platinum catalyst under suitable reforming conditions in areforming zone to produce a high octane quality gasoline material,treating a catalyst comprising about 5 to about 25% by weight ofplatinum with a hydrogen containing gas, contacting the straight chainsaturated hydrocarbon with the treated platinum catalyst at atemperature of about250 to about 420 C., a pressure of about 1 to about70 p. s. i. a., and a weight space velocity of about 0.001 to about 2thereby producing a cyclopentane compound, and combining thecyclopentane compound with the remainder of the naphtha fraction.

2. A process which comprises contacting an acyclic hydrocarboncontaining 5 to about 15 carbon atoms with a catalyst comprising about 1to about 50% by weight of platinum supported on activated charcoal, at atemperature of about 250 to about 420 C., a pressure of about 1 to about70 p. s. i. a. and a weight space velocity of about 0.002 to about 2,thereby producing a cyclopentane compound.

3. A process which comprises contacting an acyclic hydrocarboncontaining about 5 to 9 carbon atoms with a catalyst comprising about 5to about 20% platinum supported on activated charcoal, at a temperatureof about 300 to about 380 C., a pressure of about 1 to about 70 p. s. i.a. and a weight space velocity of about 0.1 to about 0.5 therebyproducing a cyclopeutanecompound.

4. A process which comprises contacting a straight chain saturatedhydrocarbon containing 5 to 15 carbon atoms with a catalyst comprisingabout 1 to about 50% by weight of platinum supported on activatedcharcoal, at a temperature of about 250 to about 420 C., a pressure ofabout 1 to about 70 p. s. i. a. and a weight space velocity of about 0.1to about 0.5 thereby producing a cyclopentane compound.

5. A process which comprises contacting a straight chain saturatedhydrocarbon containing 5 to about 9 carbon atoms with a catalystcomprising about 5 to about 25 by weight of platinum supported onactivated charcoal, at a temperature of about 300 to about 380 C., apressure of about 14 to about 40 p. s. i. a., a weight space velocity ofabout 0.1 to about 0.5 thereby producing a cyclopentane compound.

6. A process which comprises treating a catalyst comprising about 1 toabout 50% by weight of platinum sup ported on activated charcoal with ahydrogen containing gas, contacting the treated catalyst with an acyclichydrocarbon containing 5 to about 15 carbon atoms at a temperature ofabout 250 to about 420 C., a pressure of about 1 to 70 and weight spacevelocity of about 0.1 to about 0.5 thereby producing a cyclopentanecompound.

7. A process which comprises treating a catalyst comprising about 5 toabout 25% by weight of platinum supported on activated charcoal with ahydrogen containing gas, contacting the treated catalyst with an acyclichydrocarbon containing 5 to about 15 carbon atoms at a temperature ofabout 300 to about380 C., a pressure of about 14 to about 40 p. s. i.a., and a weight space velocity of about 0.1 to about 0.5 therebyproducing a cyclopentane compound.

8. A process which comprises treating a catalyst comprising about 1 toabout 50% by weight of platinum supported on activated charcoal withabout 1 to about 1000 s. c. f. b. of hydrogen, contacting the treatedcatalyst with an acyclic hydrocarbon containing about 5 to about 9carbon atoms, at a temperature of about 250 to about 420 -C., a pressureof about 1 to about 70 p. s. i. a., a weight space velocity of about0.001 to about 2 and thereby producing a cyclopentane compound.

9. A process which comprises contacting normal pentane with fixedcatalyst comprising about 1 to about 50% by weight of platinum supportedon activated charcoal at a temperature of about 250 to about 420 C. fora reaction period from about 0.5 to about 100 hours thereby producingcyclopentane.

10. A process which comprises contacting normal pentane with a fixedcatalyst comprising about to about 20% by weight of platinum supportedon activated charcoal at a temperature of about 300 to about 380 C. fora reaction period from about 0.5 to about 100 hours thereby producingcyclopentane.

11. A process which comprises contacting normal pentane with a catalystcomprising about 5 to about 20% by weight of platinum supported onactivated charcoal at a temperature of about 300 to about 380 C., apressure of about 14 to about 40 p. s. i. a. and a weight space velocityof about 0.1 to about 0.5 thereby producing cyclopentane.

12. A process which comprises contacting normal pentane with a fixedcatalyst comprising about 1 to about 50% by Weight of platinum supportedon activated charcoal at a temperature of about 250 to about 420 C. fora reaction period from about 0.5 to about 100 hours thereby producingcyclopentane.

13. A process which comprises treating a catalyst comprising about 1 toabout 50% by weight ofplatinum supported on activated charcoal withabout 1 to about 1000 's. c. f. b. of hydrogen, contacting the treatedcatalyst with normal pentane at a temperature of about 250 to about 450C., a pressure of about 1 to about 70 p. s. i. a. and a volumetric spacevelocity of about 0.001 to about 2 thereby producing cyclopentane.

14. A process which comprises subjecting a naphtha fraction containing astraight chain hydrocarbon selected from the group consisting of a Chydrocarbon, a C bydrocarbon and mixtures thereof to a separationtreatment whereby a straight chain hydrocarbon is removed therefrom,contacting the remainder of the naphtha fraction with a platinumcatalyst under suitable reforming conditions in a reforming Zone toproduce a high octane quality gasoline material, treating a catalystcomprising about 5 to about 25% by weight of platinum with a hydrogencontaining gas, contacting the straight chain saturated hydrocarbon withthe treated platinum catalyst at a temperature of about 250 to about 420C., a pressure of about 1 to about 70 p. s. i. a., and a weight spacevelocity of about 0.0001 to about 2 thereby producing a cyclopentanecompound, and passing the cyclopentane compound to the reforming zone.

15. The process of claim 14 wherein the platinum catalynst containingabout 5 to about 25 by weight of platinum is supported on activatedcharcoal.

16. A process which comprises subjecting a naphtha fraction containing astraight chain hydrocarbon selected from the group consisting of a Chydrocarbon, a C bydrocarbon and mixtures thereof to a separationtreatment whereby a straight chain hydrocarbon is removed therefrom,contacting the remainder of the naphtha fraction with a platinumcatalyst under suitable reforming conditions in a reforming zone toproduce a high octane quality gasoline material, treating a catalystcomprising about 5 to about 25 by weight of platinum with a hydrogencontaining gas, contacting the straight chain saturated hydrocarbon withthe treated platinum catalyst at a temperature of about 250 to about 420C., a pressure of about 1 to about p. s. i. a, and a weight spacevelocity of about 0.001 to about 2 thereby producing a cyclopentanecompound, and combining the cyclopentane compound with the high qualitygasoline material.

17. A process which comprises subjecting a naphtha fraction containingan acyclic hydrocarbon selected from the group consisting of thosehaving 6 or more carbon atoms to a separation treatment whereby theacyclic hydrocarbon is removed therefrom, contacting the acyclichydrocarbon with a catalyst containing about 1 to about 50% by weight ofplatinum at a temperature of about 250 to about 420 C., a pressure ofabout 1 to about 70 p. s. i. a. and a weight space velocity of about 0.1to about 0.5, thereby producing a cyclopentane compound, charging theremainder of the naphtha fraction and the cyclopentane compound to areforming zone wherein it is contacted with a reforming catalyst underconditions such that a high octane gasoline material is produced.

18. A process which comprises subjecting a naphtha fraction containingnormal pentane to a separation treatment whereby normal pentane isremoved therefrom, contacting the remainder of the naphtha fraction witha platinum catalyst under suitable reforming conditions in a reformingzone to produce a high octane quality gasoline material, treating acatalyst comprising about 5 to about 25 by weight of platinum with ahydrogen containing gas, contacting the normal pentane with the treatedplatinum catalyst at a temperature of about 250 to about 420 C. and apressure of about 1 to about 70 p. s. i. a. thereby producingcyclopentane and passing the cyclopentane to the reforming Zone.

19. A process which comprises subjecting a naphtha fraction containingnormal pentane to a separation treatment whereby the normal pentane isremoved therefrom, contacting the remainder of the naphtha fraction witha platinum catalyst under suitable reforming conditions in a reformingzone to produce a high octane quality gasoline material, treating acatalyst comprising about 5 to about 25 by weight of platinum with ahydrogen containing gas contacting the normal pentane with the treatedplatinum catalyst at a temperature of about 250 to about 420 C. and apressure of about 1 to about 70 p. s. i. a. thereby producingcyclopentane and combining the cyclopentane with the high qualitygasoline material.

References Cited in the tile of this patent UNITED STATES PATENTS2,317,683 Greensfelder Apr. 27, 1943 2,387,989 Foster Oct. 30, 19452,689,208 Murray et al. Sept. 14, 1954 2,760,912 Schwarzenbek Aug. 28,1956 OTHER REFERENCES Catalytic Isomerization of Normal Octane, by Yurveet al., Oil and Gas Journal, Aug. 11, 1938, vol. 37, No. 13, pages 55and 57.

Patent Non 2549,504 August 26, 1958 Chia ohen Cu Kang et alo of theabove numbered patent Patent should read as corrected'below.

Column 4, line 28, for 809" read a 800 g column 6, line 23, for '"OaOOZ"read 00001 5 column '7, line 46, for "000001" read 00001 column 8, line43, for "25 "read 25% o Signed and sealed this 3rd day of February 1959,

(SEAL) Attest:

KARL H AXLINE ROBERT C. WATSON Attesting Officer Commissioner of Patents

1. A PROCESS WHICH COMPRISES SUBJECTING A NAPHTHA FRACTION CONTAINING ASTRAIGHT CHAIN HYDROCARBON SELECTED FROM THE GROUP CONSISTING OF A C5HYDROCARBON, A C6 HYDROCARBON AND MIXTURES THEREOF TO A SEPARATIONTREATMENT WHEREBY A STRAIGHT CHAIN HYDROCARBON IUS REMOVED THEREFROM,CONTACTING AT LEAST THE REMAINDER OF THE NAPHTHA FRACTION WITH APLATINUM CATALYST UNDER SUITABLE REFORMING CONDITIONS IN A REFORMINGZONE TO PRODUCE A HIGH OCTANE QUALITY GASOLINE MATERIAL, TREATING ACATALYST COMPRISING ABOUT 5 TO ABOUT 25% BY WEIGHT OF PLATINUM WITH AHYDROGEN CONTAINING GAS, CONTACTING THE STRAIGHT CHAIN SATURATEDHYDROCARBON WITH THE TREATED PLATINUM CATALYST AT A TEMPERATURE OF ABOUT250* TO ABOUT 420*C., A PRESSURE OF ABOUT 1 TO ABOUT 70 P. S. I. G., ANDA WEIGHT SPACE VELOCITY OF ABOUT 0.001 TO ABOUT 2 THEREBY PRODUCING ACYCLOPENTANE COMPOUND, AND COMBINING THE CYCLOPENATE COMPOUND WITH THEREMAINDER OF THE NAPHTHA FRACTION.